2-Hydroxy-2-(1-hydroxy-2-oxoacenaphthylen-1-yl)acenaphthylen-1-one | 138858-21-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2-Hydroxy-2-(1-hydroxy-2-oxoacenaphthylen-1-yl)acenaphthylen-1-one
• CAS: 138858-21-6
• 化学式: C₂₄H₁₄O₄
• 分子量: 366.373
• InChiKey: MQPPCYTWYJJCMG-UHFFFAOYSA-N

物化性质

• 沸点：
  641.4±55.0 °C(predicted)
• 密度：
  1.611±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  28
• 可旋转键数：
  1
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  74.6
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  苊醌 在 1-methoxy-1-(trimethylsilyloxy)ethene 作用下， 以 乙腈 为溶剂， 反应 18.0h， 以49%的产率得到2-Hydroxy-2-(1-hydroxy-2-oxoacenaphthylen-1-yl)acenaphthylen-1-one
  参考文献：
  名称：

  1,2-二酮与甲硅烷基乙缩醛的光加成反应。β-羟基-γ-酮酸酯的形成

  摘要：

  研究了1,2-二酮与甲硅烷基烯酮缩醛之间的光化学反应及其激发态反应机理。观察到辐照含有1,2-二酮和甲硅烷基乙烯酮缩醛的苯，丙酮或乙腈溶液可促进1,4-二恶烯的形成，这是由[4 + 2]-环加成，氧杂环丁烷引起的，是由Paterno-Buchi过程产生的，和SET促进的Claisen型缩合反应生成的β-羟基-γ-酮酸酯。从1,2-二酮的激发态到这些产物的这些竞争途径受溶剂极性以及甲硅烷基烯酮缩醛和1,2-二酮性质的影响。克莱森（Claisen）型缩合过程遵循SET的去甲硅烷基化途径，并且在极性溶剂乙腈中进行光反应时占主导地位，

  DOI：

  10.1021/jo800473x

文献信息

• Photochemical reactions of 1,2-diketones with silyl enol ethers
  作者：Hea Jung Park、Ung Chan Yoon、Sung Hong Kim、Youngku Sohn、Dae Won Cho、Patrick S. Mariano

  DOI：10.1007/s11164-013-1203-3

  日期：2015.1

  that UV irradiation-induced photoaddition reactions of the 1,2-diketones, acenaphthenequinone, 9,10-phenanthrenequinone, and benzil, with silyl enol ethers derived from propionaldehyde and isobutyraldehyde take place to form a variety of adducts. Product formation in these cases takes place mainly via two mechanistic pathways, one initiated by single electron transfer (SET) and the other by [2 + 2]-cycloaddition

  摘要 当前研究的结果表明，紫外线辐射引起的1,2-二酮，，9,10-菲醌和苯与丙二醛和异丁醛衍生的甲硅烷基烯醇醚发生光加成反应，形成了多种加合物。 。在这些情况下，产物的形成主要通过两种机理途径进行，一种途径是通过单电子转移（SET）引发，另一种途径是通过[2 + 2]-环加成反应。此外，观察结果表明，这些途径之间的竞争取决于底物的性质。对烯醌的光反应的探索表明，当二甲基取代的甲硅烷基烯醇醚用作反应物时，光诱导的SET是主要过程，当单甲基取代的甲硅烷基烯醇醚用作底物时，环加成反应和其他激发态反应与SET竞争。在9,10-菲醌的情况下，无论所用甲硅烷基烯醇醚的性质如何，光反应都是通过[4 + 2]-环加成路线进行的。最后，在两种甲硅烷基烯醇醚的存在下照射苯甲腈导致由[2 + 2]-环加成和光诱导的苯甲酰基自由基形成α-裂解产生的产物的排他或主要形成。 图形概要
• Photoaddition reactions of acenaphthylenedione with .alpha.-silyl n-electron donors via triplet single electron transfer desilylation and triplet hydrogen atom abstraction pathways
  作者：Ung Chan Yoon、Yong Chul Kim、Jeong Ja Choi、Dong Uk Kim、Patrick S. Mariano、In Seop Cho、Yoon Tag Jeon

  DOI：10.1021/jo00031a020

  日期：1992.2

  Studies have been conducted to explore single electron transfer (SET) induced photoaddition reactions of acenaphthylenedione (ACND) with the n-electron donors Et2NCH2SiMe3, n-PrSCH2SiMe3, EtOCH2SiMe3, EtCO2CH2N(CH2Ph)CH2SiMe3, and EtCO2CH2N(CH2Ph)CH3. Photoaddition of alpha-silyl amine Et2NCH2SiMe3 to ACND occurs in CH3OH and CH3CN to produce 2-hydroxy-2-[(diethylamino)methyl]acenaphthylen-1-one. In contrast, photoaddition of n-PrSCH2SiMe3 to ACND generates two photoadducts, 2-hydroxy-2-[(n-propylthio)methyl]acenaphthylen-1-one and 2-hydroxy-2-[(n-propylthio)(trimethylsilyl)methyl]acenaphthylen-1-one, along with a ACND photoreduction dimer. Photoaddition of EtOCH2SiMe3 to ACND produces two diastereomers of 2-hydroxy-2-[ethoxy(trimethylsilyl)methyl]acenaphthylen-1-one along with the reduction dimer. The formation of all photoproducts in these photoreactions is quenched by oxygen, indicating that the triplet of ACND is the reactive excited state. Based on a consideration of the oxidation potentials of the alpha-silyl n-electron donors, and the nature of photoproducts, mechanisms for these photoadditions involving triplet SET-desilylation and triplet H atom abstraction pathways are proposed. Photoaddition of EtCO2CH2N(CH2Ph)CH2SiMe3 to ACND provides two major products, 2-hydroxy-2-[[N-benzyl-N-(carbethoxymethyl)amino]methyl]acenaphthylen-1-one and 2-hydroxy-2-[[N-benzyl-N-[(trimethylsilyl)methyl]amino]carbethoxymethyl]acenaphthylen-1-one along with several minor products. The formation of the major products via sequential SET-deprotonation pathways shows that the electron-withdrawing carbethoxy substituent serves to control the regioselectivity for deprotonation of the amine radical cation intermediate. Results obtained from the study of the photoaddition of the non-silicon-containing amino ester, EtCO2CH2N(CH2Ph)CH3, also demonstrate the effect of electron-withdrawing carbethoxy substituent on amine radical cation deprotonation regiochemistry.
• Photoaddition Reactions of 1,2-Diketones with Silyl Ketene Acetals. Formation of β-Hydroxy-γ-ketoesters
  作者：Dae Won Cho、Hyang-Yeol Lee、Sun Wha Oh、Jung Hei Choi、Hea Jung Park、Patrick S. Mariano、Ung Chan Yoon

  DOI：10.1021/jo800473x

  日期：2008.6.1

  Photochemical reactions taking place between 1,2-diketones and silyl ketene acetals and their excited state reaction mechanisms have been explored. Irradiation of benzene, acetone, or acetonitrile solutions containing 1,2-diketones and silyl ketene acetals is observed to promote formation of 1,4-dioxenes, resulting from [4 + 2]-cycloaddition, oxetanes, arising by Paterno−Buchi processes, and β-hydroxy-γ-ketoesters

  研究了1,2-二酮与甲硅烷基烯酮缩醛之间的光化学反应及其激发态反应机理。观察到辐照含有1,2-二酮和甲硅烷基乙烯酮缩醛的苯，丙酮或乙腈溶液可促进1,4-二恶烯的形成，这是由[4 + 2]-环加成，氧杂环丁烷引起的，是由Paterno-Buchi过程产生的，和SET促进的Claisen型缩合反应生成的β-羟基-γ-酮酸酯。从1,2-二酮的激发态到这些产物的这些竞争途径受溶剂极性以及甲硅烷基烯酮缩醛和1,2-二酮性质的影响。克莱森（Claisen）型缩合过程遵循SET的去甲硅烷基化途径，并且在极性溶剂乙腈中进行光反应时占主导地位，